(z)-7-{(1r,2s)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopent-3-enyl}-hept-5-enoic acid methyl ester → (z)-7-{(1r,2s)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-3-vinyl-cyclopentyl}-hept-5-enoic acid methyl ester

HRID 602729Notes

Reaction equation

HRID 602729 reaction equation
[CH:1]([Mg]Br)=[CH2:2].[CH3:5][O:6][C:7](=[O:40])[CH2:8][CH2:9][CH2:10]/[CH:11]=[CH:12]\[CH2:13][C@H:14]1[C:18](=[O:19])[CH:17]=[CH:16][C@@H:15]1/[CH:20]=[CH:21]/[C@@H:22]([O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34])[CH2:23][CH2:24][C:25]1[S:26][C:27]([CH3:31])=[C:28]([Br:30])[CH:29]=1>C1COCC1.[Cu]I>[CH3:5][O:6][C:7](=[O:40])[CH2:8][CH2:9][CH2:10]/[CH:11]=[CH:12]\[CH2:13][C@H:14]1[C:18](=[O:19])[CH2:17][CH:16]([CH:1]=[CH2:2])[C@@H:15]1/[CH:20]=[CH:21]/[C@@H:22]([O:32][Si:33]([C:36]([CH3:37])([CH3:39])[CH3:38])([CH3:34])[CH3:35])[CH2:23][CH2:24][C:25]1[S:26][C:27]([CH3:31])=[C:28]([Br:30])[CH:29]=1

Participants

5

Reactant 2

HCID 16655598(z)-7-{(1r,2s)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopent-3-enyl}-hept-5-enoic acid methyl esterHCID 178418507HCID 178418507, compound

Product 1

HCID 67215428(z)-7-{(1r,2s)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-3-vinyl-cyclopentyl}-hept-5-enoic acid methyl esterYield 79%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Vinylmagnesium bromide (1.25 mL, 1.25 mmol, 1 M/THF) was added to a 0° C. mixture of CuI (158 mg, 0.83 mmol) in 2 mL THF. The dark mixture was stirred for 5 min. and then was cooled to −78° C. A solution of Enone 7 (169 mg, 0.28 mmol) in 1 mL THF was added by cannula, rinsing with 0.25 mL THF. The mixture was stirred for 1.5 h and then 20 mL saturated NH4Cl was added. The resulting mixture was stirred for 20 min. and then was extracted with ethyl acetate (3×20 mL). The combined ethyl acetate solution was dried (Na2SO4), filtered and evaporated. Purification by flash chromatography on silica gel (7.5% ethyl acetate/hexanes) gave the title ketone (138 mg, 0.22 mmol, 79%).

Workup

  1. washrinsing with 0.25 mL THF
  2. stirringThe mixture was stirred for 1.5 h
  3. addition20 mL saturated NH4Cl was added
  4. stirringThe resulting mixture was stirred for 20 min.
  5. extractionwas extracted with ethyl acetate (3×20 mL)
  6. dry with materialThe combined ethyl acetate solution was dried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated
  9. customPurification by flash chromatography on silica gel (7.5% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-68fa3fa0bcb047739f68a5c8afcee8bc
Source dataset
uspto-grants-2011_03
Patent number
US07906552B2

Reaction notes

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